Construction,analytical study and application of a new chloramine-t selective electrode

A chloramine-T (CAT) selective electrode with a liquid membrane of nickel batho-phenanthroline—chloramine-T dissolved in 2-nitro-p-cymene is described. The liquid membrane electrode exhibits rapid and near Nernstian response to chloramine-T activity from 10^-1 to 10^-4 M. The response is unaffected by pH in the range 5–9. Major interferences are penodate and perchlorate. In analytical applications, direct potentiometnc methods for the determination of chloramme-T, ascorbic acid, and arsenic(III), and a titnmetric method for ascorbic acid are described. Ascorbic acid and arsenic(IU) in the ranges 0.4–40 and 0.5–2 mg, respectively, can be determined with relative errors of 1–2%. The method has been applied to the determination of ascorbic acid in pharmaceutical preparations.     

Spectrophotometric determination of bio-active compounds with chloramine-T and gallocyanine

A simple, sensitive and selective method for the spectrophotometric determination of drugs, viz., sulphamethoxazole, tetracycline HCl, amidopyrine, nifurtimox and isoniazid and biologically important amino acids, cysteine, aspartic acid and arginine based on their reactivity with chloramine-T (CAT) is proposed. The method involves the addition of excess CAT of a known concentration in the presence of 0.25 M HCl and the determination of the unreacted CAT by measurement of the decrease in the absorbance of the dye, gallocyanine (lambda(max): 540 nm), the most suitable of several dyes that were tested. This method was applied to the determination of drug contents in pharmaceutical formulations and to the measurement of the aspartic acid content of some protein hydrolysates. The method is useful for the determination of the target compounds in microgram quantities from 0.4-5.6 microg mL(-1) with the exceptions of arginine (1.0-8.0 microg mL(-1)) and nifurtimox (0.8-5.6 microg mL(-1)). Standard deviations were typically 0.5 mg per dose (RSD 0.5-1.2%). No interferences were observed from common excipients in formulations, and detailed interference studies of other amino acids in the determination of cysteine, aspartic acid and arginine are reported. The validity of the method was tested against spectrophotometric and titrimetric reference methods. Recoveries were 99.8-102.1%.     

Kinetic study of the determination of hydrazines, isoniazid and sodium azide by monitoring their reactions with 1-fluoro-2,4-dinitrobenzene, by means of a fluoride-selective electrode

A kinetic potentiometric method is described for the determination of hydrazines (hydrazine, phenylhydrazine, hydralazine and procarbazine), isoniazid and sodium azide, based on monitoring their reactions at 25 degrees and pH 9.0 with 1-fluoro-2,4-dinitrobenzene by means of a fluoride-selective electrode. Initial-rate and fixed-time methods were used to construct calibration graphs, generally over the range 1 x 10(-4)-1 x 10(-2)M. Hydralazine, procarbazine and isoniazid were determined in commercial formulations with a precision and error of 2-3% and the results were comparable with those of the official methods. The presence of common excipients and concomitant drugs in combination products do not interfere and the method can be used for coloured and cloudy sample solutions. A kinetic study of the reactions was made and the overall second-order rate constants are given. Base catalysis was observed. The fluoride-selective electrode is shown to be a valuable tool for monitoring fluoride-liberating organic reactions in kinetic studies and kinetic analysis.     

Amperometric determination of sodium hydrogen sulphite with chloramine-T

Amperometric titrations with chloramine-T at a rotating platinum electrode (RPE) and a dropping mercury electrode (DME) have been applied to the determination of sodium hydrogen sulphite over the concentration range 0.004-0.1N. With the RPE, the indirect titration is best, at pH between 3 and 6, whereas the DME can be used for either direct or indirect titrations, at pH around 7. Relative standard deviations of 0.5% were obtained by both methods, with relative errors not exceeding +/- 1%.     

Poly(amidosulfonic acid) modified glassy carbon electrode for determination of isoniazid in pharmaceuticals

Amidosulfonic acid was electropolymerized by cyclic voltammetry onto the surface of glassy carbon electrode (GCE) to fabricate the chemically modified electrode, which showed high stability, good selectivity and reproducibility for determination of isoniazid. The modified electrode showed an excellent electrocatalytical effect on the oxidation of isoniazid. Under the optimum conditions, there was a good linear relationship between anodic peak current and isoniazid concentration in the range of 5.0 x 10(-8)- 1.0 x 10(-5) M, and a detection limit of 1.0 x 10(-8) M (S/N = 3) was obtained after 120 s at the accumulation potential of - 0.2 V (vs. SCE). This developed method had been applied to the direct determination of isoniazid in injection and tablet samples with satisfactory results.     

Use of ion-selective electrodes in kinetic flow injection: determination of phenolic and hydrazino drugs with 1-fluoro-2,4-dinitrobenzene using a fluoride-selective electrode.

A flow injection (FI) kinetic potentiometric method for the determination of phenolic (acetaminophen and isoxsuprine) and hydrazino (isoniazid) drugs is described. This work shows the usefulness of ion-selective electrodes as detectors in FI systems, not only for direct ion determination but also in routine kinetic analysis. The method is based on the reaction of 1-fluoro-2,4-dinitrobenzene (FDNB) with the analytes in a weakly alkaline medium, which proceeds through the liberation of fluoride from the reagent. The slow reactions with phenols are catalysed by micelles of cetyltrimethylammonium bromide. The reaction rate is monitored with a fluoride-selective electrode in a wall-jet configuration and is used to construct a calibration graph of antilog(delta E/S)-1 versus c (where E = potential, s = slope of the electrode and c = concentration), using the fixed-time approach. The response time and the long-term stability of the electrode were found to be adequate for such kinetic determinations. The proposed method overcomes problems associated with end-point spectrophotometric methods using FDNB and allows measurements in highly coloured or turbid solutions. The optimized method has a linear concentration range of 1 x 10(-4)-50 x 10(-4) mol dm-3, a measurement throughput of 20 or 40 per hour and the precision ranges from 1.8 to 3.6% relative standard deviation (n = 3). Results obtained for commercial pharmaceutical formulations compare favourably with those given by reference methods.     

异烟肼在多壁碳纳米管修饰碳糊电极上的电化学行为及其应用

通过研究异烟肼在多壁碳纳米管修饰碳糊电极上的电化学行为建立了测定异烟肼的电化学方法。在pH6.8的磷酸氢二钠–柠檬酸缓冲溶液中,异烟肼在–1.114 V处能产生一明显还原峰,异烟肼在修饰电极上的反应是受吸附控制的2质子、2电子电极反应过程。研究发现还原峰峰电流大小与异烟肼浓度在5.00×10~(-3)~5.00 mmol/L内呈良好的线性关系,相关系数r=0.997 0,方法检出限为1.70×10~(-3) mmol/L,测定结果的相对标准偏差为3.11%(n=5),回收率为97.6%~103.6%。该方法简单、灵敏,精密度高,可应用于样品中异烟肼的测定。     

Amperometric detection of chloramine-T based on its reaction with <Emphasis Type="Italic">p</Emphasis>-aminophenylboronic acid

The authors describe a method for amperometric determination of chloramine-T that is based on the indirect detection of chloramine-T by detecting p-quinone imine (p-QI) that is generated by oxidation of p-aminophenylboronic acid by chloramine-T. p-QI can be detected with excellent selectivity and at low potential by using a glassy carbon electrode. Hence, the method displays attractive features such as high sensitivity, wide detection range and excellent selectivity. The electrode has two linear responses in the 50 nM to 100 μM concentration range and a 6 nM detection limit. Compared to other electrochemical methods, this assay has a detection limit that is better by three orders of magnitude. The relative standard deviation is 3.4% for the determination of 10 μM of the medical chloramine-T sample, and the recovery of a samples containing chloramine-T at a level of 10 μM is 115%.

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Graphical abstract Highly sensitive electrochemical detection of chloramine-T is achieved based on the reaction of chloramine-T with p-aminophenylboronic acid with a detection limit of 6 nM.

     

Multi-walled carbon nanotube paste electrode for selective voltammetric detection of isoniazid

A multi-walled carbon nanotube paste electrode (MWCPE) is prepared as an electrochemical sensor with high sensitivity and selectivity in responding to isoniazid. The electrochemical oxidation of isoniazid is investigated in buffered solution by cyclic and differential pulse voltammetry. The electrode is shown to be very effective for the detection of isoniazid in the presence of other biological reductant compounds. The electrochemical oxidation of cysteine, due to the high overvoltage, is completely stopped at the surface of MWCPE. The electrode exhibits a very good resolution between the voltammetric peak of isoniazid and the peaks of ascorbic acid (AA) and dopamine (DA). A resolution of more than 450 mV between the anodic peak potentials makes the MWCPE suitable for simultaneous detection of isoniazid in the presence of AA or DA in clinical and pharmaceutical preparations. Differential pulse voltammetry (DPV) is applied as a sensitive method for the determination of isoniazid. The linear range in these determinations is 1 × 10⁻⁶–1 × 10⁻³ M for isoniazid and the detection limit is 5 × 10⁻⁷ M. The electrode was applied to the simultaneous determinations in isoniazid and AA mixtures and also, isoniazid and DA mixture over a wide concentration range. The slope variation for the calibration curves of isoniazid (RSD) was less than 4.5% (based on ten measurements over a period of three months).     

Pre-concentration of indolic compounds at a carbon paste electrode and indirect determination of L-tryptophan in serum by adsorptive stripping voltammetry

The pre-concentration of indole and other indolic compounds of biochemical and pharmaceutical interest at a carbon paste electrode (Nujol/graphite) has been studied. All the compounds examined can be determined, by direct voltammetric measurements in their solutions, in the concentration range 1-8 microM. Indole, methylated indoles, harmaline and serotonin were accumulated at the electrode by a combined adsorption/extraction process. By applying the medium-exchange procedure, the accumulated compounds can be determined in the same concentration range, after a 60-s pre-concentration period, enhancing, therefore, the selectivity of the voltammetric determination. A procedure for the indirect determination of L-tryptophan in serum has been developed, which is based on these findings. L-Tryptophan was cleaved to indole by tryptophanase, and indole was subsequently determined voltammetrically after a 2-min pre-concentration period at the carbon paste electrode. From 0.3 to 1.2 micrograms of L-tryptophan in a total of 75 microliters of serum sample (20-80 microM) can be determined with an average error of ca. 0.03 microgram, whereas the recovery of added L-tryptophan in serum samples is in the range 105-115%.     

Chemically modified carbon paste electrode for iodide determination on the basis of cetyltrimethylammonium iodide ion-pair.

A new carbon paste electrode (CPE) for the determination of iodide ion based on a cetyltrimethylammonium iodide (CTMAI) ion pair as an electroactive material is described. The electrode shows a linear response for iodide ion over the concentration range of 4 x 10(-5) M to 1 x 10(-1) M with a lower detection limit of 4 x 10(-5) M at 25 degrees C. The electrode has a Nemstian slope of -55.0 +/- 0.4 mV/decade and a fast potential response of 45 s, which is almost constant over a pH range of 5.0 - 9.0. Selectivity coefficient data of the CTMAI-CPE for some common ions show negligible interference, and the electrode has high selectivity towards the iodide ion. An average recovery of 101.83% with a relative standard deviation of 1.53% has been achieved for the determination of iodide in Flaxedil (gallamine triethiodide) ampoules, a muscle relaxant drug. The electrode has been examined for the determination of iodide in saline water; the results were found to compare favorably with those obtained using Metrohm iodide ISE. The electrode has been utilized as an end-point indicator electrode for the determination of Hg(II) and phenylmercury(I) in their aqueous solutions using potentiometric titration with a potassium iodide standard solution.     

Poly(vinyl chloride) matrix membrane electrode for the selective determination of heroin (diamorphine) in illicit powders

The potentiometric response characteristics of a poly(vinyl chloride) membrane electrode for heroin based on its ion-pair complex with tetraphenylborate were examined. The influence of pH, temperature and time on the performance of the electrode system was investigated. The electrode shows a near-Nernstian response over the heroin concentration range 10(-2)-10(-4) M with good precision. The mean relative standard deviation for the determination of heroin in 40 micrograms ml-1(-1) mg ml-1 aqueous heroin hydrochloride solutions is 1.2%. The electrode exhibits good selectivity for heroin in the presence of a number of adulterants and basic organic compounds commonly present in illicit heroin powders. The method was applied to the direct potentiometric determination of heroin in illicit powders (10-36% heroin) and the results agreed fairly well with those obtained by gas - liquid chromatography.     

Titrimetric determination of chloramine-T and some aldoses by amplification reactions

A titrimetric method with amplification has been worked out for the determination of chloramine-T and certain aldoses. It is based on Leipert determination of iodide produced in the case of chloramine-T by reduction of the determinand with excess of iodide, and extraction and subsequent reduction of the iodine liberated. In the other case, the aldoses are oxidized with iodine, the surplus oxidant is extracted, and the residual iodide is determined. The method is applicable to chloramine-T in the range 0.01-3 mg, with a relative error between -3.0 and -0.4% and a relative standard deviation of 0.6-0.8%, depending on the amount present, and to 0.05-1 mg of glucose, galactose or arabinose, or 0.1-2 mg of lactose or maltose, with a relative standard deviation of 1.4% for > 0.5 mg of aldose.     

Kinetic determination of EDTA and citrate by the displacement of fluoride from Al(3+)F(-) complexes and use of a fluoride ion-selective electrode

The displacement of fluoride from its aluminium complexes by the action of EDTA, citrate and other ligands is a relatively slow process which can be monitored potentiometrically with a fluoride ion-selective electrode. Some characteristics of these reactions are presented. There is evidence that [AlF](2+) reacts with the competitive ligand faster than the simple free (hydrated) Al(3+) species does. The relative rates of release of fluoride by the action of various aminopolycarboxylic acids have been determined. Potentiometric reaction-rate methods have been developed for the determination of 0.2-1.5 mumole of EDTA and 0.1-1.0 mumole of citric acid, with average relative errors of approximately 3%.     

Ion-selective electrode for aluminum determination in pharmaceutical substances, tea leaves and water samples

A novel ion-selective PVC membrane sensor for Al(III) ions based on 6-(4-nitrophenyl)-2-phenyl-4-(thiophen-2-yl)-3,5-diaza-bicyclo[3.1.0]hex-2-ene (NTDH) as a new ionophore has been prepared and studied. The electrode exhibit a good response for aluminum ion over concentration range of 1.0x10(-6) to 1.0x10(-1) mol L(-1) with a Nernstian slope of 19.6+/-0.4 mV per decade and low detection limit of 6.3x10(-7) mol L(-1). The best performance was obtained with membrane composition 30% poly(vinyl chloride), 62% acetophenone, 5% oleic acid, 3% ionophore and 2 ml tetrahydrofuran. NTDH-based electrode was suitable for aqueous solutions of pH 3. It has relatively fast response time (approximately 10 s) and can be used at least for 3 months without any considerable divergence in potentials. The proposed membrane electrode revealed good selectivity for Al(III) ions over a wide variety of other cations. The standard electrode potentials were determined at different temperatures and used to calculate the isothermal coefficient of the electrode. The formation constant and stoichiometry ratio of ionophore-Al(III) complex were calculated at 25 degrees C by using segmented sandwich membrane method. It was used in non-aqueous solvents and also as indicator electrode in potentiometric determination of Al(III) ions in some real samples.     

Design of an optical sensor for indirect determination of isoniazid

The characterization of an optical sensor membrane is described for indirect determination of isoniazid. The sensing membrane was consisted of immobilized 3-(2-pyridyl)-5,6-diphenyl-1,2,4-triazine (PDT) on a triacetylcellulose membrane. The procedure is based on the reaction of Fe(III) with isoniazid in the presence of PDT. Fe(III) is reduced by isoniazid to Fe(II) which forms a complex with PDT. The complex shows an absorption maximum at 558nm. By measuring the absorbance of the complex at this wavelength, isoniazid can be determined in the range of 0.62-6.15mugmL(-1). This method was applied to the determination of isoniazid in pharmaceutical formulation and enabled the determination of isoniazid in microgram quantities.     

A flow injection chemiluminescence system for the determination of isoniazid

A chemiluminescence (CL) flow system is described for the determination of isoniazid based on its enhancement on the chemiluminescence (CL) emission produced upon mixing a hexacyanoferrate(III) solution with an alkaline luminol solution. The system responds linearly to isoniazid concentration in the range 0-1 mg/L with a detection limit (3sigma) of 0.03 microg/L, relative standard deviation (RSD) of 1.2% for 0.1 mg/L isoniazid (n = 11). The system has been successfully applied to the determination of isoniazid in pharmaceutical preparations.     

Determination of artemether in plasma and whole blood using HPLC with flow-through polarographic detection

An HPLC method with polarographic detection for the trace determination of artemether in plasma and whole blood was developed and applied to pharmacokinetic and clinical pharmacological studies. The method showed high sensitivity and selectivity because of the easy reduction of the peroxide linkage of artemether at the mercury drop electrode. The detection limit was 10 ng and the detector response was linear over the range of 10 ng to 1 microgram artemether injected onto the column. The largest relative standard deviation of 10 replicate measurements of standard solutions (concentrations of 10 ng/mL-1 microgram/mL) was 8%. The recovery from whole blood and plasma of added drug (concentrations of 15-480 ng/mL) was 71-100%.     

流动注射后化学发光法测定异烟肼

本文发现了异烟肼在铁氰化钾-钙黄绿素化学发光反应体系中的后化学发光反应。优化了反应条件,建立了一种利用后化学发光反应测定异烟肼的流动注射化学发光分析法。方法的检出限为6×10-8g/mL, 相对标准偏差为1.8% (2.0×10-6 g/mL 异烟肼,n=11）,线性范围为2.0×10-7~1.0×10-5 g/mL。此法已用于异烟肼片剂中异烟肼含量的测定,结果与药典方法测定值一致。     

Potentiometric titration of fluoride,sulfate, chromate,molybdate, tungstate,oxalate, phosphate,pyrophosphate and hexacyanoferrate(II) ions with lead(II) solutions and a fluoride-selective electrode

A semi-automatic potentiometric method is described for the direct titration of fluoride with lead(II) solutions in the presence of added chloride. Sulfate, chromate, molybdate, tungstate, oxalate, phosphate, pyrophosphate, and hexacyanoferrate(II) are titrated similarly in the presence of added chloride and fluoride. A fluoride-selective electrode is used to detect the end-points. Fluoride in the range 0.57–5.7 mg can be determined with a precision of about 0.3%. The other ions can be determined in the range 0.025–0.30 mmol with a precision of 0.5–1%.